Azo-dyestuffs



tion:--

Patented July 16, 1935 A ZO-DYESTUFFS Gerald Bo'nhte, Basel, Switzerland, assignor to the 'firm Society of Chemical Industry in Basle,

Basel, Switzerland No Drawing. Application December 21, 1934, SerialiNo. 758,703. In Switzerland January 23, 193 i j 6 Claims. (01. 260-95) This invention relates to the manufacture of valuable new dyestufis by coupling an arylide oi the 2,3-hydroxynaphthoic acid with a'diazotized base of the general formula 7 r in which R is a benzene nucleus which may contain various substituents (for example, halogen, alkyl, alkoxy or N -acy1) The dyestufis produced 1 are blue-red to Bordeaux-red, garnet red and violet. Thesame tints are produced on the fiber by the dyestuffs and have excellent properties of fastness.

The diazotizing components here in question may be made, for example, quite generally, by

acylation and reduction of condensation products obtainable from compounds such as 2 -nitro-l,4- dihalogen-S-aminobenzene and phenol or a nuclear substitution product thereof, such as ortho-,

'paraor meta-cresol, ortho-, para-' or meta-chlorrophenol, a chlorocresol, -a dichlorophenol, a mono-alkyl ether of hydroquinone or resorcinol or pyrocatechol, chloroguaicol or the like.

As acylating agents there may be named acetic anhydride, acetyl chloride, chloro-acetyl chloride, chlorocarbonic ester, propionyl chloride, benzoyl chloride, the chlorobenzoyl chlorides, phthalic anhydride, and'the like. M v The following examples illustrate the inven- 1 Example 1 27.6 parts: by weight of 4 -Ch1OI0-2-3.mlll0-5 acetylamino-l,ldiphenylether are diaz otized in the usual manner. The clear diam-solution is introduced into a solution consisting of 27.7 parts of 2,3-hydroxynaphthoic' acid-para toluidide, parts of sodium hydroxide solution of 30 per cent. strength, 15 parts of sodium carbonate and 2000 parts of water. The dyestuff thus produced, very probably corresponding with the formula.

separates immediately in the form of a Bordeauxred precipitate which is filtered and dried.

Example 2 1 liter. oped in a neutralized solution containing 2 grams of diazotized 4-chloro 2-amino-5-acetylaminol,l'-diphenylether per liter. There is produced a pureiBordeaux-red tint of excellent properties, of fastness. Thenew dyestuff very probably corresponds with the formula Like Bordeaux-red tints are, obtained when there is used the para-chloranilide, the ,B-naphthalide, the para-phenetidide, the 2,4-dimethoxyl 5e *Cottonyarn is impregnated with a grounding i prepared-by dissolving 7 grams of 2,3-hydroxynaphthoic acid-2-methoxy-5-chloranilide in 3001 i cc. of hot water with addition of 12 cc. oisodium hydroxide solution of 30 per cent. strength [and 10 cc. of Turkey red oil, and diluting the whole to The yarn is then wrung out and devel 5-chloranilide, the2-methoxy-5-methylani1ide of 2,3-hydroxynaphthoic acid. Garnet red tints of like excellent properties oi fastness are obtained when other arylides of 2,3-hydroxynaphthoic acid are used; for example, 5-chloro-2-toluidide; 3 ,4- dichloranilide. 1:

I H Example 3 :7 Cotton yarn .is. impregnated with a solution 7 grams of 2,3-hydroxynaphthoic acid-para; chloranilide, 14 cc. of sodium hydroxide solution of 30 per cent. strength and 10 cc. of Turkey red oil' -per.1iter;. it is. then wrung out anddeveloped-in a diazo-solution neutralized withLso-- dium carbonate and containing 2 vgrams,,;of.;. 4-chloro-2-amin0-5a.cetylamino-4methyl l,1 diphenyletherper liter and is finally rinsed and. soaped. There isobtained a pure Bordeaux-red tint of :verygood properties of. fastncssr -fIFh new dyestufi very probably corresponds with the formula a -OH r10 OHM v p Like tints are obtainedwith other arylides of 2,3-hydroxynaphthoic acid, for example, with the anilide, the a- 'orfi-naphthalide, the orthoanisidide,v the ortho-tolui'dide, the 2.-methyl-4 anisidide, the 2,5-dimethoxyanilide of 23-mdroxy-naphthoic acid.

Garnet red tints are produced whenv 4- or 5-chlo-ro-2-toluidideor meta-nitranilide of 2,3

hydroxynaphthoic acid isused. 1

' Example 4 Gotton yarn is impregnated in 25 timesits weight of a'sol-ution 0255- grams of 2 ,'3'-hydroxynaphthoic acid-2,5-dimethoxyanilide, 1 0-cc. of

sodium hydroxide solution of '30 per cent;

strength, 10 cc. of Turkey red oil, 5 cc. of formaldehyde solution of' lO per cent. strength per liter at 25-30 C.; it is then well wrung out and developed in a solution bufiered with sodium acetate and containing 2 grams of diazotized nylether per liter. Rinsing and soaping follow.

4A-dichloro-2-amino 5-acetylamino-1,l diphe- There is obtained a very pure Bordeaux-red tint of excellent properties of fastness. The new dyestufi very probably corresponds with the formula similar' Bordeaux-red tints are obtained: when other arylides of 2,3-hydroxynaphthoic acidare;

used, for example, the Z-methoxyanilide, the 4-ethoxyanilide, the 2,4-dimethoxy-5-ohloranilide, the l-chloro-Z-anisidide, the Z-chloranilide Zf-naphthylarhid of 2,3-bydroxynaphthdlc acid. 1. h

' The material to-be printed is iowlardedwithz. an alkaline solution containing per liter 12 of 2,3-hydroxynaphthoicacid-Q-ani'siididn. 1 After drying, the material is printed withla printing colour containing 8 grams: 0t diazotized' r-chime 2--amino-5-acetylaminok' xhethoxY-hT-diphee nylether per kilo; l The pure Bordeaux-red color develops quickly and is very fast. The new dyestuff very probably corresponds with nnm'ula' wherein R1 stands forabenzenenucleus; and- R2 for an aryl radical of the or HBjih f thal'ene' series; which products form dark powders dissolving in sulfuric acid to a violet solutionami in pyridine to a red solution, and dye cotton fast vivid violet to Bordeaux-red tints.

' 2; The dyestuffs of the general formula i 1 l on N-n wherein R1 stands for a benzene nucleus and R2 for an aryl radical of the benzene or naphthalene series, which products form dark powders dissolving insulfuric acid to a violet solution and in pyridine to a red solution, and dye cotton fast vivid Bordeaux-red tints.

not

3. The dyestuffs of the general formula. 5. The azo-dyestufi of the formula,

H CH ("i-N-H CHaCIIT-H C1 O OlQOO-Ol N u N N OH on f f tiO O H o H which product forms a dark powder dissolving in wherem R2 Stands for an aryl radlcal the sulfuric acid to a. violet solution and in pyridine zene or naphthalene series, which products form to a red solution, and dyes cotton fast Vivid dark powders dissolving in sulfuric acid to a Bordeaux red tints. violet solution and in pyridine to a red solution, The azo d estuff of the formul and dye cotton fast vivid Bordeaux-red tints. y a

4. The azo-dyestuff of the formula II OHa-C-N-H which product forms a, dark powder dissolving in which product forms a dark powder dissolving in sulfuric acid to a, violet solution and in pyridine sulfuric acid to a, violet solution and in pyridine 'to a red solution, and dyes cotton fast vivid to 21'. red solution, and dyes cotton fast vivid aux-red t ts- Bordeaux-red tints. GERALD BONHOTE. 

